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Syntheses, Characterization, and Reactivity of Diruthenium Hydrido Complexes

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journal contribution
posted on 06.04.2016, 19:18 authored by Heather R. Wiltse, Alyssa N. Johnson, Raphael J. Durand, William Brennessel, Robert M. Chin
The reaction of [cis-{(η5-C5H3)2(CMe2)2}­Ru22-4,4′-di-tert-butyl-2,2′-bipyridine)2­(MeCN)2]­[OTf]2, 1, with H2 yields a μ-dihydrido complex, [cis-{(η5-C5H3)2(CMe2)2}­Ru22-4,4′-di-tert-butyl-2,2′-bipyridine)2­(μ-H)2]­[OTf]2, 2, in 79% yield. The reaction of 2 with Et3SiH affords a mono-μ-hydrido complex, cis-{(η5-C5H3)2(CMe2)2}­Ru22-4,4′-di-tert-butyl-2,2′-bipyridine)2­(μ-H)]­[OTf], 3. The reaction of either 2 or 3 (1–2 mol %) with C6H6 and Et3SiH results in the catalytic cleavage of the C–H bond in benzene along with the cleavage of the Si–Et bond to form PhEt2SiH (23–27% conversion) and C2H6. The reaction of 2 or 3 (1 mol %) with THF and Et3SiH results in the cleavage of the C–H bond in THF followed by the insertion of the SiEt2 group into the C–O bond, forming 2,2-diethyl-1-oxa-2-silacyclohexane (14% conversion) as one of the products.

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